CN105826560A - Preparation method of SiOx-based lithium ion battery composite anode material - Google Patents

Preparation method of SiOx-based lithium ion battery composite anode material Download PDF

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Publication number
CN105826560A
CN105826560A CN201610390247.8A CN201610390247A CN105826560A CN 105826560 A CN105826560 A CN 105826560A CN 201610390247 A CN201610390247 A CN 201610390247A CN 105826560 A CN105826560 A CN 105826560A
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Prior art keywords
sio
lithium ion
preparation
ion battery
composite cathode
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Inventor
张均营
李传波
郑军
左玉华
薛春来
成步文
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Institute of Semiconductors of CAS
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Institute of Semiconductors of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a preparation method of a SiOx-based lithium ion battery composite anode material. The preparation method includes the following steps that a SiOx material is subjected to high-energy ball milling treatment, and the size of the SiOx material is reduced; the SiOx material obtained after ball milling treatment is evenly mixed with a C precursor polyacrylonitrile (PAN) according to a certain proportion, slurry is prepared, a copper current collector is coated with the slurry, and a round electrode is prepared after drying is conducted; the round electrode is subjected to pyrolysis treatment, and the SiOx@C composite anode material is obtained. The method is simple in preparation process and low in cost, and a battery has good cycling performance.

Description

A kind of SiOxThe preparation method of base lithium ion battery composite cathode material
Technical field
The present invention relates to technical field of lithium ion, especially a kind of SiOxThe preparation method of base lithium ion battery composite cathode material.
Background technology
Portable electric appts, electric automobile and energy-storage system to high-energy-density, high-specific-power, the long-life, low cost secondary cell demand more and more urgent.Lithium ion battery, due to its numerous advantage, becomes the leading role that secondary energy sources field receives much concern.
The performance of battery depends primarily on electrode material.Si sill, as lithium ion battery negative material, can form Li with lithium22Si5Alloy, has the highest specific discharge capacity (up to 4200mAhg-1), it is the most commonly used graphite (372mAhg-1) ten times more than of material.And it has relatively low removal lithium embedded current potential (about 0.1-0.3VvsLi/Li+), low with the reactivity of electrolyte, and cost is relatively low, it is provided that the advantages such as the longest discharge platform.But, owing in charging process, Si material can occur huge volumetric expansion (about 400%), this will cause between electrode material and electrode material separates with collector, and then loses electrical contact, thus causes capacity to decay rapidly, and cycle performance deteriorates rapidly.
The specific capacity higher due to silica-based protoxide and good cycle performance, have recently received great interest and study.Lithium ion first with SiOxLi can be produced during reaction2O and Li4SiO4, it as buffering composition, thus can suppress Si volumetric expansion in cyclic process to a certain extent, thus improve cycle performance.
Summary of the invention
(1) to solve the technical problem that
Present invention aim at providing a kind of simple SiOxThe preparation method of base lithium ion battery composite cathode material, the method preparation technology is simple, low cost, it is easy to accomplish large-scale production, and cycle performance of battery is excellent.
(2) technical scheme
For reaching above-mentioned purpose, the invention provides a kind of SiOxThe preparation method of base lithium ion battery composite cathode material, comprises the steps: step 1: to SiOxMaterial carries out high-energy ball milling process, reduces SiOxThe size of material；Step 2: according to a certain percentage by the SiO after ball-milling treatmentxMaterial uniformly mixes with C presoma polyacrylonitrile (PAN), makes slurry, is coated on copper current collector, makes circular electrode after drying；Step 3: circular electrode is carried out pyrolysis processing, obtains SiOxC composite negative pole material.
In such scheme, described SiOxMaterial is for the main active substances as composite cathode material for lithium ion cell, and x is 0.1-1.8, SiOxThe particle diameter of material is 1 μm-100 μm.
In such scheme, described to SiOxMaterial carries out high-energy ball milling process, ratio of grinding media to material 30: 1 to 10: 1, and rotating speed is 10-5000r/min, and the time is 1h-30h.
In such scheme, described to SiOxAfter material carries out high-energy ball milling process, SiOxThe particle diameter of material is reduced to about 1 μm by original maximum 100 μm, and particle size distribution becomes uniform.
In such scheme, described step 2 includes: be 2: 8 to 8: 2 by the SiO after ball-milling treatment according to mass ratioxMaterial uniformly mixes with C presoma polyacrylonitrile (PAN), obtains slurry, is coated on copper current collector by this slurry, and the thickness of film is 10 μm-250 μm, is dried 8h-12h, is prepared as circular electrode at 90 DEG C-120 DEG C.
In such scheme, described circular electrode is carried out pyrolysis processing, be heat treatment 1h-3h at 400 DEG C-600 DEG C.
In such scheme, the method is obtaining SiOxAfter C composite negative pole material, also include: to the SiO obtainedxC composite negative pole material carries out lithium battery assembling, and carries out cycle performance test.
(3) beneficial effect
The SiO that the present invention providesxThe preparation method of base lithium ion battery composite cathode material, uses high-energy ball milling method to reduce SiOxScantling, and by mixing with C presoma polyacrylonitrile (PAN), make slurry, it is coated on copper current collector, makes circular electrode after drying, and carry out pyrolysis processing, thus obtain SiOxC composite negative pole material.The above-mentioned preparation method that the present invention proposes, is combined by simple high energy ball mill method and is thermally treated resulting in SiOxC composite negative pole material, SiOxReduced size and lithium ion first with SiOxLi can be produced during reaction2O and Li4SiO4, can the most effectively inhibit bulk effect as buffering composition.The surface C cladding formed can suppress the change in volume in cyclic process further, and improves SiOxElectric conductivity, thus be effectively increased the cycle performance of lithium battery.
Accompanying drawing explanation
In order to the concrete technology contents of the present invention is described, describe in detail below in conjunction with diagram, wherein:
Fig. 1 is the SiO that the present invention providesxThe preparation method flow chart of base lithium ion battery composite cathode material.
Fig. 2 is SiOxThe SEM picture of (b) before (a) and ball milling after ball milling；
Fig. 3 is the SiO obtained after high-energy ball milling method combines heat treatmentxC composite negative pole material correspondence lithium ion battery charge/discharge cycle characteristics.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, and referring to the drawings, the present invention is described in more detail.
The present invention proposes a kind of simple SiOxThe preparation method of base lithium ion battery composite cathode material, makes SiO by high-energy ball milling methodxSize effectively reduces, and by mixing with C presoma polyacrylonitrile (PAN), makes slurry, is coated on copper current collector, makes circular electrode after drying, and carries out pyrolysis processing, obtains SiOxC composite negative pole material.
The SiO that the present invention proposesxThe preparation method of base lithium ion battery composite cathode material, with SiOxFor original material, combine heat treatment by simple high energy ball mill method, effectively reduce SiOxSize, and obtain SiOxC composite construction.Preparation technology is: first by SiOxMaterial high-energy ball milling method processes certain time under certain rotating speed.Smaller size of SiO will be obtainedx, mix with C presoma PAN, make slurry, be coated on copper current collector, make circular electrode, and heat treatment after drying, form SiOxC composite negative pole.The method preparation technology is simple, low cost, is suitable for large-scale production, and its cycle performance of battery is stable.
As it is shown in figure 1, the embodiment of the present invention provides a kind of SiOxBase negative material and the preparation method of lithium battery thereof, comprise the steps:
Step 1: to SiOxMaterial carries out high-energy ball milling process, reduces SiOxThe size of material；
In this step, SiOxMaterial is for the main active substances as composite cathode material for lithium ion cell, and x is 0.1-1.8, SiOxThe particle diameter of material is 1 μm-100 μm；To SiOxMaterial carries out high-energy ball milling process, ratio of grinding media to material 30: 1 to 10: 1, and rotating speed is 10-5000r/min, and the time is 1h-30h；To SiOxAfter material carries out high-energy ball milling process, SiOxThe particle diameter of material is reduced to about 1 μm by original maximum 100 μm, and particle size distribution becomes uniform；
In one embodiment of the invention, the SiO of 1-3g is takenx, add in high-energy ball milling ball grinder, add ball milling ball by ratio of grinding media to material 30: 1-10: 1；Under 200-800rpm rotating speed, ball milling 5-10h；As in figure 2 it is shown, Fig. 2 is SiOxSEM figure before and after material ball milling, by the SiO of particle diameter about 50 μmxMaterial carries out high-energy ball milling process, SiO after ball millingxThe particle diameter of material is reduced to about particle diameter 1 μm by 50 original μm and particle size distribution are uneven.
Step 2: according to a certain percentage by the SiO after ball-milling treatmentxMaterial uniformly mixes with C presoma polyacrylonitrile (PAN), makes slurry, is coated on copper current collector, makes circular electrode after drying；
In this step, it is 2: 8 to 8: 2 by the SiO after ball-milling treatment according to mass ratioxMaterial uniformly mixes with C presoma polyacrylonitrile (PAN), obtains slurry, is coated on copper current collector by this slurry, and the thickness of film is 10 μm-250 μm, is dried 8h-12h, is prepared as circular electrode at 90 DEG C-120 DEG C；
Step 3: circular electrode is carried out pyrolysis processing, obtains SiOxC composite negative pole material；
In this step, circular electrode is carried out pyrolysis processing, be heat treatment 1h-3h at 400 DEG C-600 DEG C.
The method is obtaining SiOxAfter C composite negative pole material, also include: to the SiO obtainedxC composite negative pole material carries out lithium battery assembling, and carries out cycle performance test.As it is shown on figure 3, be SiOxThe lithium ion battery charge/discharge cycle characteristics figure that C composite negative pole is corresponding.First all reversible capacities of electrode reach 1559.7mAh/g, due to lithium ion and SiOxLi can be produced during reaction2O and Li4SiO4, therefore first all coulombic efficiencies are relatively low, but it can effectively buffer Si bulk effect in cyclic process, and the raising to stable circulation is very helpful.The introducing of C can be while suppressing the bulk effect in cyclic process further, the SiO being effectively improvedxElectric conductivity.After 100 charge and discharge cycles, reversible capacity is up to 1071.7mAh/g, and coulombic efficiency is up to 99.8%.
Particular embodiments described above; the purpose of the present invention, technical scheme and beneficial effect are further described; it is it should be understood that; the foregoing is only the specific embodiment of the present invention; it is not limited to the present invention; all within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. done, should be included within the scope of the present invention.

Claims (7)

1. a SiOxThe preparation method of base lithium ion battery composite cathode material, it is characterised in that comprise the steps:
Step 1: to SiOxMaterial carries out high-energy ball milling process, reduces SiOxThe size of material；
Step 2: according to a certain percentage by the SiO after ball-milling treatmentxMaterial uniformly mixes with C presoma polyacrylonitrile (PAN), makes slurry, is coated on copper current collector, makes circular electrode after drying；
Step 3: circular electrode is carried out pyrolysis processing, obtains SiOxC composite negative pole material.
SiO the most according to claim 1xThe preparation method of base lithium ion battery composite cathode material, it is characterised in that described SiOxMaterial is for the main active substances as composite cathode material for lithium ion cell, and x is 0.1-1.8, SiOxThe particle diameter of material is 1 μm-100 μm.
SiO the most according to claim 1xThe preparation method of base lithium ion battery composite cathode material, it is characterised in that described to SiOxMaterial carries out high-energy ball milling process, ratio of grinding media to material 30: 1 to 10: 1, and rotating speed is 10-5000r/min, and the time is 1h-30h.
SiO the most according to claim 1xThe preparation method of base lithium ion battery composite cathode material, it is characterised in that described to SiOxAfter material carries out high-energy ball milling process, SiOxThe particle diameter of material is reduced to about 1 μm by original maximum 100 μm, and particle size distribution becomes uniform.
SiO the most according to claim 1xThe preparation method of base lithium ion battery composite cathode material, it is characterised in that described step 2 includes:
It is 2: 8 to 8: 2 by the SiO after ball-milling treatment according to mass ratioxMaterial uniformly mixes with C presoma polyacrylonitrile (PAN), obtains slurry, is coated on copper current collector by this slurry, and the thickness of film is 10 μm-250 μm, is dried 8h-12h, is prepared as circular electrode at 90 DEG C-120 DEG C.
SiO the most according to claim 1xThe preparation method of base lithium ion battery composite cathode material, it is characterised in that described circular electrode is carried out pyrolysis processing, is heat treatment 1h-3h at 400 DEG C-600 DEG C.
SiO the most according to claim 1xThe preparation method of base lithium ion battery composite cathode material, it is characterised in that the method is obtaining SiOxAfter C composite negative pole material, also include:
To the SiO obtainedxC composite negative pole material carries out lithium battery assembling, and carries out cycle performance test.
CN201610390247.8A 2016-06-02 2016-06-02 Preparation method of SiOx-based lithium ion battery composite anode material Pending CN105826560A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107302080A (en) * 2017-06-21 2017-10-27 天津爱敏特电池材料有限公司 A kind of silica-base film negative material and preparation method thereof
EP3828981A4 (en) * 2018-07-26 2022-04-20 Mitsui Chemicals, Inc. Nonaqueous electrolyte solution for batteries and lithium secondary battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103035917A (en) * 2013-01-09 2013-04-10 北京科技大学 Preparation method of silicon dioxide/ carbon composite negative electrode material for lithium ion battery
CN103236517A (en) * 2013-04-26 2013-08-07 中国东方电气集团有限公司 Lithium ion battery silicon-based negative material and preparation method thereof
CN104538607A (en) * 2014-12-19 2015-04-22 天津巴莫科技股份有限公司 Preparation method of silicon-carbon negative electrode material for lithium ion battery

Patent Citations (3)

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CN103035917A (en) * 2013-01-09 2013-04-10 北京科技大学 Preparation method of silicon dioxide/ carbon composite negative electrode material for lithium ion battery
CN103236517A (en) * 2013-04-26 2013-08-07 中国东方电气集团有限公司 Lithium ion battery silicon-based negative material and preparation method thereof
CN104538607A (en) * 2014-12-19 2015-04-22 天津巴莫科技股份有限公司 Preparation method of silicon-carbon negative electrode material for lithium ion battery

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107302080A (en) * 2017-06-21 2017-10-27 天津爱敏特电池材料有限公司 A kind of silica-base film negative material and preparation method thereof
EP3828981A4 (en) * 2018-07-26 2022-04-20 Mitsui Chemicals, Inc. Nonaqueous electrolyte solution for batteries and lithium secondary battery
US12095037B2 (en) 2018-07-26 2024-09-17 Mitsui Chemicals, Inc. Non-aqueous electrolyte solution for battery and lithium secondary battery

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